Method for polymeric surface modification

ABSTRACT

Polymers, and particularly conventional commodity bulk polymers, are modified to have a surface activity of interest using a surface modifying polymer that includes a moiety that favors migration to the surface of the bulk polymer together with a moiety provides the activity of interest (e.g., biocidal, wettability modifying (hydrophobic or hydrophilic), resistance to radiant energy, providing a functional group for functionalizing the surface, etc.). The surface modifying polymer is combined with the bulk polymer, and, due to the presence of the moiety that favors migration, concentrates primarily on the surface of the bulk polymer such that the moiety that provides the activity of interest is located primarily on the surface of the bulk polymeric article which is produced.

CROSS-REFERENCE TO RELATED APPLICATIONS

This patent application is related to U.S. Provisional Application60/485,494 filed Jul. 9, 2003, and the complete contents of thatapplication is herein incorporated by reference.

This invention was made using grants from the U.S. Government,particularly NSF (523279), DARPA (528979), and the government may havecertain rights under the patent.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to a method for modifying thesurface of conventional commodity polymers, including without limitationpolyurethanes, polyesters, polyethers, polyamides, polyimides, etc.

2. Background Description

Surface modification of a polymeric article is performed or attemptedfor a number of different reasons. For example, it may be desirable tohave a bulk polymer that has a surface that is modified to better accepta paint or dye, or to have a surface that imparts a property such asresistance to chemical or radiant energy damage.

A number of different methods have been developed for modifying thesurfaces of a polymer. Many of these methods involve post processing ofthe article. For example, the polymeric article may be exposed to aplasma, or a plasma processing step followed by grafting of compounds tothe surface of the polymer. Also, the polymeric article might besubjected to a chemical or radiant energy exposure to alter the surface.It is known to combine a fluorinated polymer with a conventional polymerto get the surface-concentrated fluoropolymer. (Ji, Q.; Kang, H.; Wang,J.; Wang, S.; Glass, T. E.; McGrath, J. E., Surface characterization offluorinated oxetane polyol modified polyurethane block copolymers,Polymer Preprints, 2000, 41, 346-347.) It is known that combining afluorinated group with a UV absorbing chromophore surface-concentratesthe chromophore.(Vogl, O.; Jaycox, G. D.; Hatada, K., Macromoleculardesign and architecture, Journal of Macromolecular Science-Chemistry,1990, 27, 1781-1854.) It is known that combining a perfluorohexyl groupwith a fullerene surface-concentrates the fullerene at a styrene airinterface. (Chen, W.; McCarthy, T. J., Adsorption/migration of aperfluorohexylated fullerene from the bulk to the polymer/air interface,Macromolecules, 1999, 32, 2342-2347.)

SUMMARY OF THE INVENTION

It is therefore an object of the invention to provide polymeric articlesor coatings, and methods of making polymeric articles or coatings, wherethe polymeric article has a surface phase having an activity ofinterest.

According to the invention, there is provided a methodology forpreparing polymer articles or coatings which have a surface phase withan activity of interest. It is understood that a telechelic is anoligomeric or polymeric material with reactive groups usually at thechain ends and may also be called a macromonomer. In the methodology, asurface active telechelic or polymer is prepared which includes both asurface active segmer which favors migration to the surface of a bulkpolymer and one or more functional segmers which provide an activity ofinterest (e.g., biocide, bioactive, UV protective, hydrophobic,hydrophilic, etc.). When combined with bulk polymer, the surface activesegmers bring the functional segmers to the surface of the polymericarticle during processing (e.g., creation of a coating, extruding,etc.). In one embodiment, the surface modifying additive are one or moretelechelics that contain fluorinated surface-active segmers andfunctional segmers or one or more polyurethanes comprised ofconventional hard block forming units (diisocyanates and diols and/ordiamines) and soft blocks that contain fluorinated surface-activesegmers and functional segmers. The surface-active segmers bring thefunctional segmers to the surface and together these segmers constitutethe functional surface-active soft block of the surface modifiers (SMs).To demonstrate a specific embodiment in a broad range of possiblefunctional SMs, biocidal SMs have been prepared by preparingpolyurethane SMs comprised of isophorone diisocyanante/butane diol hardblocks and soft blocks comprised of fluorinated segmers (surface active)combined with biocidal moieties (function) in soft blocks. Afteractivation, these SMs effectively kill pathogen challenges on contactdemonstrating the efficacy of the SM concept. Additional examplesdemonstrate that SMs confer unusual wetting behavior on the substratepolymer. Such tailored change may find use in biomaterials, filters,cosmetics, and other areas where surface properties such as feel andcapability to attract moisture are important. It is understood in thecontext of this patent, that the terms telechelic and macromonomer areused interchangeably. Furthermore, it is understood that when astatement is made such as “telechelic in the polyurethane” that theterminal reactive groups present on the telechelic are no longer presentbut changed to appropriate functionality by virtue of incorporation(e.g, a urethane group if reaction occurs between an alcohol group onthe telechelic with an isocyanate on the hard block).

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other objects, aspects and advantages will be betterunderstood from the following detailed description of a preferredembodiment of the invention with reference to the drawings, in which:

FIG. 1 is a schematic generalized representation of a surface activemodifier and bulk substrate;

FIG. 2 is a schematic representation of a surface active functional softblock;

FIG. 3 is a schematic flow diagram showing monomer modification byintroducing functional groups, and copolymerizing to form a telechelic;

FIG. 4 is a schematic flow diagram representation showing theincorporation of the macronomoner of FIG. 3 into a polymer to form asurface modifying additive (SMA) polymer which contains themacromonomer;

FIG. 5 is a schematic flow diagram showing the subsequent modificationof the SMA of FIG. 4 to introduce a desired functionality;

FIG. 6 is a schematic representation of a polyurethane surface modifier;

FIG. 7 is a schematic diagram showing surface functionalization via theinventive SMA approach illustrated by the addition of 2% gen-1-SMA(PU-SMA 2) to and IPDI/BD/PTMO polyurethane (PU-1), where the conversionof near surface amide to a chlorimide SMA-Cl, is highlighted in a box atthe top;

FIG. 8 shows the chemical structure and ¹H-NMR spectrum of PU-1containing ME3Ox-ran-3FOx copolymer soft segment in DMSO-d6;

FIG. 9 a-f show typical tapping-mode AFM images of polyurethane films.PU-3: containing PTMO (a,b), PU-1: containing ME3Ox-ran-3FOx (c,d), andPU-2: containing ME3Ox-block-3FOx (e,f); (a,c,e): height images at z=10nm, and (b,d,f): phase images at z=20°; Rms: (a) 0.6 nm, (c) 0.3 nm, and(e) 0.9 nm; Tapping force (A/A₀): (a,b) 0.87, (c,d) 0.83, and (e,f)0.92;

FIG. 10 shows AFM images in combination with contact angle and XPS datawhich demonstrate the phase separated nanoscale morphology ofMDI/BD/(ME3Ox-block-3F)(1:1), PU-2 shown in FIG. 9 f is conferred at a2% loading level to conventional MDI/BD(36)/PTMO polyurethane;

FIG. 11 is a schematic drawing showing the contraphilic properties ofSMs of the present invention;

FIG. 12 is a composite of photographs and a graph showing force versusdistance for contraphilic polyurethane containing hydantoin substitutedpoly(oxetane) soft blocks;

FIG. 13 shows a schematic representation of the AATCC-100 test discussedin Example 5 for demonstrating biocidal activity;

FIG. 14 shows bacterial challenge (E. coli) results obtained using theSMA modified bulk polymers of the present invention; and

FIG. 15 shows the P. aeruginosa challenge results.

DETAILED DESCRIPTION OF A PREFERRED EMBODIMENT OF THE INVENTION

The general concept of a surface modification contemplated by thepresent invention is shown in FIG. 1. The objective is to modify thesurface of a coating or molded object, referred to generically as apolymeric article 10 to include a surface domain 12 which has a propertyof interest without affecting the bulk properties in the bulk domain 14.

The invention generally relates to polymeric additives that act tomodify the surface properties of conventional commodity polymers. Thisis achieved by synthesis of polymeric surface modifiers (SMs), sometimesreferred to as surface modifier additives (SMAs) with a structure thatfavors migration to the surface of a bulk polymer. In particular, thesurface-philic character of the SMs depends on the presence of afunctional block, which is preferably a “soft block” or flexible chainsegment that contains a surface-active segmer and a functional segmer.The approach leverages the general tendency of soft blocks to surfacesegregate, the presence of surface active groups such as fluorinatedgroups (inclusive of fully fluorinated or semifluorinated groups [e.g.,—(CH₂)n(CF₂)mF, —(CH₂)n(CF₂)mH) where n is typically 1-10 and m istypically 1-12] in the soft segment, and the synergistic combination ofsurface-philic soft blocks with a multiplicity of surface active groups.

A general structure for such a soft block is shown in FIG. 2. The exactembodiment will depend on the commodity or bulk polymer chosen formodification. In particular, an air philic group 16, such as asemifluorinated group, is combined in the soft block with one or morefunctional moieties 18 and 20 shown for exemplary purposes as function 1and function 2, respectively. The telechelic may have reactive endgroups 22 which may polymerize with monomers for the purpose ofincorporation into an SMA as shown in FIG. 4. The telechelic block isitself preferably a polymer where the number of repeat units 26 m+n+p ispreferably more than one for each unit, and most preferably rangingbetween 2 and 200 for each unit. The functional soft block may be usedalone or incorporated in a segmented copolymer to effect the preparationof a new kind of SM. The SM is added to a commodity polymer or “base”polymer that has desired bulk properties. The resulting blend isrepresented schematically in FIG. 1. The SM determines the surfaceproperties by virtue of concentration of the SM at the surface, orair-polymer interface 28 as shown in FIG. 2, during ordinary processingconditions such as coating or extrusion.

There are two general ways that an SM may be employed. One is literallyas an additive. That is, the SM is added to some substrate system suchas a liquid or solid coating composition. A second way is to spray orcoat an extremely thin film on an already formed object such as a filter(e.g., the SM alone or with the bulk polymer are sprayed or coated ontothe surface of a filter with the SM migrating to the surface of thecoating). In either case, the combination of properties provided by thesoft block structure illustrated in FIG. 2 will assure that the functionof interest will be surface concentrated.

The SM of this invention is generated in different ways. One methodstarts with the synthesis of monomers with suitable functions, thepolymerization of monomers to co-macromonomers (co-telechelics), and thegeneration of an SM by incorporating the co-macromonomers into apolymer. A second method involves the modification of an SM polymer togenerate the desired functional SM.

With reference to FIGS. 3 and 4, the circle represents a cyclic monomersubstrate; R or R¹ preferably represents a reactive functional groupintroduced in ring opening polymerization such as the hydroxy group —OHor amino group —NH₂; P is the mole fraction of monomer containingfunction F1; A and B are polymer forming moieties such as isocyanatesand alcohol terminated chain extenders (reactive groups R² and R³),respectively, for polyurethane formation for example, isocyanates andamine terminated chain extenders for polyurethane urea formation forexample, or only monomer or polymer “A” might be needed (e.g., adicarboxylic acid) for ester formation, for example.

With reference to FIG. 3, the SM may be generated by synthesizingmonomers F1 and F2 (F2 may itself be synthesized by similar proceduresused for F1), and then copolymerizing the monomers. This creates amacromonomer having F1 and F2 functions, and the macromonomer itself maybe a soft block or polymer. In a preferred embodiment, the macromonomeris incorporated into (e.g., polymerized with or grafted on, etc.)another polymer at either or both of its end groups R to form thedesired SM. See, for example, the creation of a copolymer with monomersA and B and the macromonomer containing F1 and F2 in FIG. 4. In thepresent invention, either F1 or F2 must be a segmer which preferentiallymigrates to the surface of a polymer during casting, extrusion, coating,etc. Once formed, the macromonomer (FIG. 3) and/or polymer containingthe macromonomer (FIG. 4) which separately or together are the surfacemodifiers (SM) is mixed (typically 2% by weight or less) into a desiredbase polymer to give a solid with a modified surface as shown in FIG. 1.

FIG. 5 shows an existing SM containing macromonomer (e.g., a polymercontaining A, B, and soft block containing F1 and F2) being modified toinclude a desired functionality F3. Here, a desired functionality F3 isintroduced by reaction of an existing SM with Fn to give a new SMpolymer. Supposing that Fn reacts with F2 to give F3, the reaction maybe complete, in which case q is zero. However, if Fn reacts with F2 togive F3, the reaction may be incomplete, in which case q is finite andthe macromonomer (SM polymer) contains three functional repeat units F1,F2, and F3. Examples of Fn include pre-biocidal moieties such as5,5-dimethylhydantoin, hydrophilic groups such as polyethylene oxidemoieties (e.g., CH₃O(CH₂CH₂O)n-, where n=0-15), alcohols (such as—CH₂)nOH), or where n=1-10); and/or amines, such as —(CH₂)nNH₂, wheren=1-10), chromophoric groups, alkylammonium groups (that may havebiocidal character) such as (—NH₂(CH₂)nH)⁺, where n=1-20, andcombinations (“libraries”) of these groups to generate surfaces withspecialized properties such as wetting behavior, response to acidicand/or basic conditions or selective detection of target molecules,and/or biocidal activity.

Another example of Fn is a group that has protected functionality suchas a —Si(OR)₃ group (R=—(CH₂)nH, where n=1-5, and includes Me, Et,isopropyl, propyl, etc., acetato, and other hydrolysable groups). By“protected” is meant that upon exposure to a suitable reagent, achemical change takes place that produces a new kind of functionality.In the case of —Si(OR)₃, exposure to moist air or mild acid produces the—Si(OH)₃ group which is hydrophilic and can undergo a crosslinkingreaction to produce a siliceous domain by well known condensationreactions releasing water. This importance of this approach is that a—Si(OH)₃ group would normally not migrate to the air polymer interfaceas it is a high energy group that prefers to remain in the bulk.

The functional group F2 (or F3) could be a trimethylsilyl or similargroup such as an oligosiloxane (—(CH₂)n[Si(Me₂)O]mSiMe₃). Thiscotelechelic may have some unusual combination of hydrophobic/oleophobicbehavior as surface active groups such as semifluorinated groups (F1)are oleophobic and hydrophobic, but groups such as trimethylsilyl (oroligo-siloxane) are only hydrophobic (but not oleophobic).

In testing the new approach to surface functionalization contemplated bythis invention, the C—Br group has been introduced as a modelfunctionality, and is described in detail in Example 1. Another group ofmacromonomers containing CH₃O(CH₂CH₂O)n- has been prepared to test thesurface modified additive approach of the present invention, and isdescribed in detail in Examples 2 and 3. Examples 1, 2 and 3 fall intoclass I described by FIG. 3 (co-monomers→cotelechelic→polyurethane SMAwith cotelechelic-derived soft block). Examples 4 and 5 describe a“reaction on polymer” approach as described in FIG. 5.

In one embodiment, the SMs can be polyurethanes. Polyurethanes (PU) areused in a variety of applications, and are an excellent model for thegeneral application of the present invention because of their broad useand robust character. The general scheme for polyurethane surfacemodifiers is shown in FIG. 6, where a bulk polyurethane 30 is combinedwith a surface modifier 32 which contains an active group, a functionalgroup, and a compatibilizing hard block to yield a product 34 with afunctional group concentrated at the coating surface. In this specificembodiment of the general concept, surface active and functional groupsare incorporated into the soft block. This approach takes advantage ofboth surface concentration of soft blocks and surface-philicity offluorinated groups. Further details are provided in Examples 4 and 5.

The specific functionality incorporated in the soft block in Example 1is a reactive —C—Br group. In Examples 2 and 3, a hydrophilic ethyleneoxide moiety is introduced. In Example 4, a hydantoin,5,5-dimethylhydantoin is introduced, which confers on the surface of theSMA itself unusual wetting behavior. In Example 5, thesurface-concentrated pre-biocide depicted in FIG. 7 is reacted withbleach to generate surface concentrated, biocidal chloramide function.However, it should be understood that a wide variety of functionalities(that is groups other than the F3 (FIG. 5) prebiocidal hydantoin group)could be used in the practice of this invention including withoutlimitation the groups noted above.

In order to obtain surface-active telechelics bearing reactive groups,co-telechelics containing semifluorinated and bromomethyl groups can beprepared. 3-bromomethyl-3-methyloxetane (BrOx) is readily available andoffers a reactive group for subsequent derivitization. Homo- andco-polymerization of BrOx with 3FOx (—CH₂CF₃) and 5FOx (—CH₂CF₂CF₃) iscontemplated in this exemplary process. Using the FOx/BrOx telechelics,polyurethanes were prepared employing isophorone diisocyanate(IPDI)/butane diol (BD) hard blocks. Most work was done using a 40% hardblock polyurethane IPDI-BD(40%)-3FOx/BrOx(1:1), where 40% is percenthard block and 1:1 signifies the mole ratio of 3FOx to BrOx. Example 1provides details.

As described in Example 5, the pre-biocidal functional group5,5-dimethylhydantoin (Hy) was introduced into by a “reaction onpolymer” carried out in dimethyl formamide (DMF). FIG. 7 shows theresulting SMA 36 as IPDI-BD-(3FOx/BrOx/HyOx)(1:0.3:0.7) where HyOx is asubstituted oxetane segmer containing the hydantoin moiety. This wascombined with bulk polyurethane 38 (conventional IPDI-BD-PTMO-2000 (40%hard block) polyurethane) at 2 wt % SMA 36, 98 wt % bulk polyurethane 38mixture. The coating 38 thus formed included an SMA domain 40, and abulk polyurethane domain 42. Evidence for the surface concentration of2% SMA-98% polyurethane came from Wilhelmy plate analysis and biocidalactivity.

It will be understood that the concentration of the SMA in the polymericarticle or coating to be formed can vary depending on the application.It will typically constitute 10% or less by weight, and most preferably0.1-3 weight percent of the polymeric article or coating. Even lowerpercentages may be adequate depending on the application and the SMcomposition and processes. Some SMs are more efficient surfaceconcentrators than others.

As will be discussed below, this invention can be employed to make abiocidal SMA such that a polymeric article or coating formed accordingto the invention has an underlying bulk polymer domain and a surfacedomain having a SMA with biocidal activity. This might, for example, beespecially useful in the hospital or clinic setting wherein gloves,countertops, examining tables, surgical equipment and tools, wall paper,surfaces of computer keyboards, cellphones and pagers, and cabinetry canhave polymer coating that provides a biocidal activity. The biocidalactivity may also be useful in other settings such as schools andoffices where large numbers of people are gathered. The biocidalactivity may be useful in modifying air filters, by, for example,applying a microcoating on the filter material or creating the filterfrom the SMA and bulk polymer mixture, so as to not only trap pathogensor agents but to inactivate them.

It should be understood that the invention can be used to impart asurface domain to a bulk polymer where the surface domain has a varietyof other desired activities. For example, in automobile applications itmay be desirable to apply a polymer coating where the surface domainrepels water or corrosive agents. This would require forming an SMA withfunctional group segmers that make the surface of the polymer coatingmore repellant to water (e.g., combining both fluorinated groups (F1)with trimethylsilylated (or oligosiloxane) groups (F2) as noted abovemight be used. Conversely, in paper or sign making applications where itis desirable to accept dyes, colorants, paints, or the like, the SMAwould be formed with functional group segmers that make the polymercoating more hydrophilic (e.g., hydrophilic groups such as polyethyleneoxide moieties (e.g., CH₃O(CH₂CH₂O)n-, where n=0-15), alcohols (such as—(CH₂)nOH), or where n=1-10); and/or amines, such as —(CH₂)nNH₂, wheren=1-10) and their derived ammonium salts (as —(CH₂)nNH₃ ⁺, wheren=1-10), chromophoric groups, alkylammonium groups such as(—NH₂(CH₂)nH)⁺, where n=1-20, and combinations (“libraries”) of thesegroups to generate surfaces with specialized wetting behaviorproperties.

As another example, it may be desirable to provide a means forfunctionalizing the surface of the polymer with leaving groups (e.g.,Br) such that the surface could be derivitized with compounds ofinterest. In this instance, the invention may allow the formation ofdiagnostic chips that have DNA, RNA, amino acids, amino acid sequences,or other biological materials of interest bonded to the surface of apolymer coating by way of interaction with the functional leaving group.

As yet another example, the surface of a polymer can include afunctional segmer which enables a fluorescent, phosphorescent,chemiluminescent, or color change reaction to occur when the functionalsegmer is in contact with a particular agent. This property would findsensing/detection utility in diagnostic devices, as well as inapplications such as signs and displays. In still another application ofthe invention, fiber optics can be extruded where the surface of theoptic includes the surface-active agent, which thus encircles the core.For example, in the fiber optic application, the surface modifier mightprevent UV or other radiant energy from transmission to the core or, byvirtue of interaction with the evanescent surface wave might act as anoptical sensor/detector.

In the exemplary case of a biocidal SMA [FIG. 7, Example 5], the SMA wasprepared via the method shown in FIG. 5, wherein “A” and “B” togetherrepresent a hard block in a polyurethane (PU) derived from isophoronediisocyanate (A) and butane diol (B). The low Tg block is a copolymerwhere F1 is a fluorinated group (3-FOx) and F2 is a bromomethyl group.In this case, not all the bromomethyl groups are replaced by biocideprecursor 5,5-dimethylhydantoin (F3) so that the resulting SMA has threerepeat units (F1, the fluorinated group, F2, the unreplaced bromomethylgroups, and F3, the pre-biocidal moiety 5,5-dimethylhydantoin). Theresulting SMA has been added to a base polyurethane, treated with bleachto generate the biocidal N-Cl group (N-halamine) and tested againstseveral pathogens. N-halamines are discussed in detail in U.S. Pat. No.6,469,177 to Worley, which is herein incorporated by reference. Asdiscussed in detail in Example 5, in 30 min exposure, 99.999% or >5.2log reduction of Pseudomonas aeruginosa was observed against a suitablecontrol. This sets a minimum for biocidal activity as no survivingbacteria were found after exposure to the SMA modified PU. Similarresults were obtained for Staphylococcus aureus and E. coli.

The synthesis and characterization of nonionic detergents is well known.Such molecules have an amphiphilic structure. That is, one end of themolecule may be hydrophilic, while the other end is oleophilic.Molecules that have one hydrocarbon end one poly(ethylene oxide) end areexamples. The bifunctional telechelics described herein may find use aspolymeric nonionic detergents. For example, the block telechelicsdescribed in Example 2 have a fluorocarbon end (hydrophobic, oleophobic)and an oligomeric ethylene oxide end (hydrophilic). Such architecture isuncommon. This architecture would mediate between fluorocarbon-like andwater-like phases. For example, such a detergent might be useful inemulsifying materials that are insoluble in water, supercritical CO₂, orother solvent. Such a structure could prevent phase separation betweenimmiscible polymers.

Even the random copolymer may be useful as a nonionic detergent becauseof the extreme difference solubility parameter between fluorinatedsubstituents (that can be widely varied) and hydrophilic side chains(that can also be widely varied). This application would be novel forall binary and ternary combinations of:

-   -   Oleophilic groups such as (—CH₂)nH, tetramethylene oxide,        isomeric hydrocarbon and hydrocarbon-halocarbon (—CHxCl)H,        ketone containing, side chains    -   Hydrophilic groups such as aforementioned oligomeric and        polymeric ethylene oxide, alcohol, carboxylic acid, amine        containing side chains    -   Fluorous groups such as those aforementioned [e.g.,        —(CH₂)n(CF₂)mF, —(CH₂)n(CF₂)mH) where n is typically 1-10 and m        is typically 1-12]

In view of the contemplation of use of molten salts as reaction mediaand other applications for amphiphilic (and even triphilic) molecules,molecules with cationic (typically alkyl ammonium) or anionic (typicallycarboxylate, sulfate, sulfonate, phophonate) functionality are readilyenvisaged and could be used in combination with oleophilic, hydrophilic,and fluorous groups described above.

EXAMPLE 1

Homo- and copolymerization of BrOx and FOx monomers were carried out bya modification of the procedure reported by Malik. [Malik, A. A.;Archibald, T. G.; GenCorp: US, 2000.] Cationic ring openingpolymerization was employed with BF₃ dietherate and 1,4-butanediol ascatalyst and co-catalyst, respectively, to give the desired telechelic.A typical procedure follows.

Copolymerization of 3-trifluoroethoxy-3-methyloxetane (3FOx) and3-bromomethyl-3-methyloxetane (BrOx) monomers were carried out by amodification of a published procedure. Cationic ring openingpolymerization was employed using BF₃OEt₂ and 1,4-butanediol as catalystand co-catalyst, respectively. Methylene chloride (5.54 ml) was pouredinto a round bottom flask under nitrogen. 1,4-butanediol (0.77 g, 8.54mmol) and BF₃—OEt₂ (2.45 g, 17.27 mmol) were added into reaction mediumand stirred at room temperature for 45 min under nitrogen purge. Thenthe solution was cooled to −20° C. by using dry/aqueous isopropylalcohol mixture. Mixture of 3FOx and BrOx monomers (e.g., total 30.09 g,172.43 mmol) in methylene chloride (42.10 ml) was added drop wise withan addition rate of 170 drops/min. The reaction temperature was kept at−25 to −30° C. by addition of extra dry ice for 5 hrs. The reactionmixture was then brought to room temperature and quenched with 50 ml ofwater. The organic phase was separated, washed with 2 wt % aqueous HCland NaCl solutions and then precipitated into methanol/water mixture(5:1). The precipitated macromonomer was placed into vacuum oven forovernight drying at 50° C., 4 Torr. The product was viscous, slightlyopaque with more than 85% yield.

A number of FOx-BrOx telechelics were made by a similar procedure. Thecompositions and molecular weights are shown in Table 1 below: TABLE 1Compositions and molecular weights of telechelic poly(oxetanes). Monomerfeed ratio^(a,b) Poly(oxetane) telechelics Telechelic 3FOx 5FOx BrOxFOx:BrOx^(c) D_(p) ^(c) MW^(c,d,e) 3FOx 1.0 — — — 18.5 3400 5FOx — 1.0 —— 24.2 5660 BrOx — — 1.0 — 17.1 2820 3FOx:BrOx-1:1 1.0 — 1.0 1.2:1.027.0 4710 3FOx:BrOx-2:1 2.0 — 1.0 2.2:1.0 26.5 4700 3FOx:BrOx-1:2 1.0 —2.0 1.0:1.7 19.6 3360 5FOx:BrOx-1:1 — 1.0 1.0 1.2:1.0 20.5 40855FOx:BrOx-2:1 — 2.0 1.0 1.9:1.0 11.9 2500 5FOx:BrOx-1:2 — 1.0 2.01.0:1.8 18.1 3400^(a)Monomer/catalyst (BF₃—OEt₂) mole ratio = 10.^(b)Catalyst (BF₃—OEt₂)/cocatalyst (1,4-butanediol) mole ratio = 2.02.^(c)Determined by ¹H-NMR end group analysis.^(d)M_(w) by GPC with PS standards (universal calibration): BrOx; 2600,5FOx:BrOx-1:2; 5800, 3FOx:BrOx-1:2; 4100^(e)Polydispersities for these three telechelics by GPC were: BrOx 1.58,5FOx:BrOx-1:2; 1.35, 3FOx:BrOx-1:2; 2.04.

Table 1 lists telechelic molecular weights determined by end groupanalysis. Molecular weights were obtained by integrating the high fieldmethylene peaks next to the trifluoroacetyl group at 4.2-4.3 ppm andmethyl peaks in FOx at 0.92 ppm(CH3, FOx) and BrOx at 1.05 ppm (CH3,BrOx). In previous reports, homotelechelic molecular weights weredetermined by integrating the low field methyl peaks (due to terminalresidues) and the main chain ones [Malik, A. A.; Carlson, R. P. U.S.Pat. No. 5,637,772, 1997, which is herein incorporated by reference].Molecular weights were determined by GPC (in THF compared to PSstandards) for those telechelics not having a refractive index matchingTHF. The observed values for Mw and Mn (footnote to Table 1) values givethe following polydispersities: 1.58 for BrOx, 2.04 for 3FOx:BrOx-1:2,and 1.35 for 5FOx:BrOx-1:2. These values are similar to those previouslyreported for 3FOx and 5FOx polyoxetane telechelics polymerized using theBF3 THF/neopentyl glycol catalyst/co-catalyst system. [Kausch, C. M.;Leising, J. E.; Medsker, R. E.; Russell, V. M.; Thomas, R. R.; Malik, A.A., Synthesis, characterization, and unusual surface activity of aseries of novel architecture, water-dispersible poly(fluorooxetane)s.,Langmuir, 2002, 18, 5933-5938.]

Thermal analysis. Standard and temperature modulated DSC (MDSC) startingfrom sub-ambient temperatures were used to measure the telechelic T_(g)(Table 2). MDSC experiments were performed at a heating rate of 3°C./min with a modulation temperature of ±0.5° C./min. It is important tonote that all telechelics have low glass transition temperaturescharacteristic of polyols used as soft blocks in polyurethanes. TABLE 2Measured and calculated glass transition temperatures of homo andco-telechelics. Homo or Co-telechelic T_(g) (° C.) T_(g) (° C.)Poly(oxetane) (DSC) (Calculated^(a)) BrOx −24 — 3FOx −51 — 5FOx −48 —3FOx:BrOx-1:2 −33 −32 3FOx:BrOx-1:1 −37 −36 3FOx:BrOx-2:1 −38 −395FOx:BrOx-1:2 −34 −33 5FOx:BrOx-1:1 −36 −36 5FOx:BrOx-2:1 −39 −39^(a)From the Fox equation.Polyurethanes containing FOx-BrOx soft blocks. A number of SMpolyurethanes were synthesized. The compositions are summarized in Table3. In designating compositions, such as IPDI-BD(40)/3FOx:BrOx-1:1(4700),the hard block composition is followed with hard block wt % inparentheses. The soft block segmers are next, followed by their moleratio and M_(n) in parenthesis. The segmented PUs were synthesized in aconventional two-step procedure as shown in Scheme 2. First, an excessof IPDI was added to telechelic. When all the alcohol groups wereconsumed, BD chain extender was added until no isocyanate absorption wasdetectible by FT-IR. As the viscosity increased, DMF or THF/DMF wasadded so that the solution contained about 30-40% solids at the end ofthe reaction. PUs having different concentrations of soft block can beobtained simply by changing the ratio of telechelic to chain extender(1,4-butanediol) ratio.

The hard segment concentration was utilized was 40-45 wt %. PUs havinglower hard block content (25-35%) are mechanically very soft while thosewith higher hard block content (45-60%) are rigid. The hard blockcontent in an SM application could thus be varied to optimize compliancewith the substrate polymer.

Representative FOx-BrOx polyurethane synthesis. A typical synthesis isrepresented by the synthesis for IPDI-BD(40)/3FOx:BrOx-1:1(4700). Thepolyurethane (PU) was synthesized in 3-neck round bottom flask. Oxetanepolyol, 3FoxBrOx(1:1), (9.23 g, 1.92 mmol) was introduced into the flaskwith isophorone diisocyanate, IPDI, (4.44 g, 19.97 mmol). Dimethylformamide, DMF, (3.13 g) was added into the reaction mixture as solvent.The initial % solid was 81%. The solution was heated and stirred with anover-head stirrer under nitrogen purge and with condenser. 7 drops ofdibutyltin dilaurate catalyst, T-12, (1 wt % in toluene) was added toreaction medium when the reaction temperature was 65-70° C. The mixturewas stirred for 3 hours at this temperature range. The reaction wasfollowed by FT-IR. After 3 hours the prepolymer was ready for chainextension. 1,4 butane diol, BD, (1.61 g, 17.87 mmol) was used as chainextender. The reaction was frequently diluted with DMF as the polymermolecular weight increases. Chain extension took place at the sametemperature range (65-70° C.). The reaction was followed with FT-IR. Thereaction continued until all the isocyanate (NCO) was consumed. Thefinal PU has slightly yellow color and the final concentration of themixture was 43%. The resulting PU was then precipitated into methanolfor purification. The solution cast PU films were prepared.

Table 3 provides compositions, molecular weights, and DSC information.We were not able to synthesize a 5FOx homo-telechelic polyurethane. Thereaction mixture phase separated during the chain extension apparentlydue to the different solubility parameters of 5FOx TABLE 3 Molecularweights, and glass transitions temperatures of polyurethanes M_(n) M_(w)T_(g) ^(a) T_(g) ^(b) Phase Designation (×10³) (×10³) PD (ss) (hs)Sep^(c) IPDI-BD(50)/PTMO(2000) Base PU 23.3 52.5 2.26 −46 38 0.76IPDI-BD(40)/BrOx(2800) PU-1 19.4 42.9 2.21 −10 56 0.81IPDI-BD(40)/3FOx(3400) PU-2 17.5 37.4 2.14 −37 46 0.84IPDI-BD(40)/3FOx:BrOx-2:1(4700) PU-3 18.9 46.0 2.43 −29 73 0.89IPDI-BD(40)/3FOx:BrOx-1:1(4700) PU-4 17.9 36.8 2.05 −29 62 0.90IPDI-BD(40)/3FOx:BrOx-1:2(3400) PU-5 16.5 33.9 2.06 −24 56 0.89IPDI-BD(40)/5FOx:BrOx-2:1(2500) PU-6 18.9 40.1 2.12 −27 57 0.88IPDI-BD(40)/5FOx:BrOx-1:1(4100) PU-7 29.6 61.2 2.07 −25 64 0.89IPDI-BD(40)/5FOx:BrOx-1:2(3400) PU-8 16.6 33.8 2.04 −29 64 0.89 IPDI-BDHard Block 17.2 31.8 1.85 NA 85 na^(d)^(a)Soft segment (ss) glass transition temperature.^(b)Hard segment (hs) glass transition temperature.^(c)Weight fraction (±0.xx) soft block in the soft-segment phase,calculated by using the Fox equation.^(d)Not applicable.

-   -   soft and polyurethane hard blocks.

Molecular weights. Molecular weights, and polydispersities of the newpolyurethanes are shown in Table 3. GPC analyses gave M_(w)s in therange of 30-60,000. With one exception, M_(w)s for the FOx:BrOxpolyurethanes have somewhat lower M_(w)s compared to the conventionalPTMO analog. While molecular weights are modest, all the polyurethanesformed smooth, optically transparent coatings and freestanding films.

Wetting Behavior. Polyurethane wetting behavior was determined by theWilhelmy plate method using a Dynamic Contact Angle Analyzer (DCA). TheWilhelmy plate experiment has been discussed in connection with themeasurement of intrinsic contact angles for model PDMS networks. [Uilk,J. M.; Mera, A. E.; Fox, R. B.; Wynne, K. J., Hydrosilation-curedpoly(dimethylsiloxane) networks: Intrinsic contact angles via dynamiccontact angle analysis, Macromolecules, 2003, 36, 3689-3694.]Remarkably, all of the co-telechelic polyurethanes have higher θ_(adv)and lower θ_(rec) than the parent homo-telechelic PUs (Table 4). TABLE 4Advancing and receding contact angles for PUs. Cycle-1 Cycle-2 Cycle-3Cycle-4 Cycle-5 Water PU(ratio)^(a) Adv/Rec Adv/Rec Adv/Rec Adv/RecAdv/Rec Con. Base PU  84/55  82/55  82/56  81/56  81/56 No PU-1 102/42101/41 101/41 101/40 101/40 No PU-2 105/45  99/45  98/46  98/46  98/46Yes PU-3 (2:1) 108/35 108/35 108/35 108/34 108/34 No PU-4 (1:1) 116/33115/32 116/32 No PU-5 (1:2) 104/34 102/34 102/34 102/34 102/34 Yes PU-6(2:1) 109/38 108/38 108/38 108/38 108/38 No PU-7 (1:1) 109/35 109/35109/35 109/35 109/35 Yes PU-8 (1:2) 107/36 106/36 106/36 106/36 106/36Yes^(a)Ratio of nFOx:BrOx. n = 3 for PU-3, 4, and 5. n = 5 for PU-6, 7, and8.

The most surprising result for PU co-telechelics (θ_(adv), 116°;θ_(rec), 32°) is the wetting behavior of PU-4,IPDI-BD(40)/3FOx:BrOx-1:1(4700). These values are constant over threecycles and no water contamination is detected. The very stable contactangle hysteresis (84°) is noteworthy for topologically smooth surfaces(vida infra). Few polymers have θ_(adv) that exceed 116°.

Surface Modifying Behavior. IPDI-BD(40)/3FOx:BrOx-1:1(4700) (2%) wasadded to an ordinary IPDI-BD polyurethane containing a 2000 MWpoly(tetramethylene oxide) soft block. X-ray photoelectron spectroscopydemonstrated surface concentration of the SM by virtue of Br and Fanalysis that was similar to IPDI-BD(40)/3FOx:BrOx-1:1(4700) alone.These results demonstrate the efficacy of surface concentration of thereactive C—Br function. That is, a function which contains a Br leavinggroup that allows modification of the polymer after formation of thepolymeric article or coating.

EXAMPLE 2

Monomer synthesis. 3-(Methoxyethoxyethoxymethyl)-3-methyloxetane (ME2Ox)was synthesized using phase transfer catalysis (PTC). A mixture of2-(2-methoxyethoxy)ethanol (60.1 g, 0.5 mol), BrOx (82.5 g, 0.5 mol),TBAB (8.0 g, 0.025 mol) and water (20 ml) was stirred and heated to 75°C. Then, a solution of KOH (35.5 g, 87%, 0.55 mol) in water (50 ml) wasadded. The reaction mixture was stirred vigorously at 80-85° C. for 7hrs. The mixture was cooled to room temperature, filtered, and dilutedwith water. The product was extracted with methylene chloride anddistilled at 100° C./8 mmHg. ME2Ox monomer; ¹H-NMR (CDCl₃) δ1.32 (—CH₃,3H, s), δ3.39 (—OCH₃ 3H, s), δ3.55 (—OCH₂CH₂O—, 4H, m), δ3.67(—OCH₂CH₂O—, 4H, and —CH₂—, 2H, m), δ4.35 (ring —CH₂—, 2H, d), δ4.52(ring CH₂, 2H, d); ¹³C-NMR (CDCl₃) δ21.5 (—CH₃), δ40.0(—C—), δ59.1(—OCH₃), δ70.7, 71.1, and 72.1 (—OCH₂CH₂O—), δ76.6 (—CH₂—), δ80.2 (ring—CH₂—).

7FOx monomer was prepared from BrOx and 2,2,3,3,4,4,4-heptafluorobutanolby the same procedure used for ME2Ox monomer. 7-FOx monomer; ¹H-NMR(CDCl₃) δ1.31 (—CH₃, 3H, s), δ3.67 (—CH₂—, 2H, s), δ3.99 (—CH₂CF₂—, 2H,t), δ4.34 (ring —CH₂—, 2H, d), δ4.50 (ring —CH₂—, 2H, d)

Homo-and Cotelechelic polyoxetane synthesis. Homo- and copolymerizationof ME2Ox and FOx monomers were carried out by a modification of apublished procedure for FOx and methyloxetane. [Malik, A. A.; Archibald,T. G.; GenCorp: US, 2000.] The homotelechilic has not been previouslysynthesized and is a new composition of matter. Cationic ring openingpolymerization 3-bromomethyl-3- was employed using BF₃ and1,4-butanediol as catalyst and co-catalyst, respectively. Methylenechloride (10 ml) was poured into a round bottom flask under nitrogen.1,4-butanediol (165 mg, 1.84 mmol) and BF₃—OEt₂ (520 mg, 3.67 mmol) inmethylene chloride (10 ml) were added and stirred at room temperaturefor 45 min under nitrogen. Then the solution was cooled to 0-5° C. inice bath, and a mixture of ME2Ox and FOx monomers (e.g., total 36.7mmol) in methylene chloride (10 ml) was added dropwise at the rate of0.5 ml/min. The reaction was kept at 0-5° C. for 4 hrs with stirring.The reaction mixture was then brought to room temperature and quenchedwith 30 ml of water. The organic phase was separated, washed with 0.2%HCl and NaCl aqueous solution and then solvent was evaporated. Theproduct (a viscous, opaque liquid) was re-dissolved in acetone, andre-precipitated in water. The resulting viscous liquid was separated anddried in a vacuum oven at 70° C., 5 Torr overnight to give a transparentoily product with >80% yield.

ME2Ox homopolymer; ¹H-NMR (CDCl₃) δ0.91 (—CH₃, 3H, s), δ3.19 (backbone—CH₂—, 4H, m), δ3.30 (—CH₂—, 2H, s), δ3.38 (—OCH₃ 3H, s), δ3.55(—OCH₂CH₂O—, 4H, m), δ3.64 (—OCH₂CH₂O—, 4H, m); ¹³C-NMR (CDCl₃)δ17.3-17.9 (—CH₃), δ40.8-41.3 (backbone —C—), δ58.9 (—OCH₃), δ70.4 and71.9 (—OCH₂CH₂O—), δ70.9-71.3 (—CH₂—), δ74.0 (backbone —CH₂—).

ME2Ox/5FOx (ME2Ox/7FOx) copolymer; ¹H-NMR (CDCl₃) δ0.91 (—CH₃ for ME2Oxand FOx, 3H, s), δ3.19 (backbone —CH₂—, 4H, m), δ3.30 (—CH₂— for ME2Ox,2H, s), δ3.38 (—OCH₃ 3H, s), δ3.44 (—CH₂— for FOx, 2H, s), δ3.55(—OCH₂CH₂O—, 4H, m), δ3.64 (—OCH₂CH₂O—, 4H, m), δ3.85 (—CH₂CF₂—, 2H, t);¹³C-NMR (CDCl₃) δ16.9-17.8 (—CH₃ for ME2Ox and FOx), δ40.8-41.5(backbone —C—), δ58.6 (—OCH₃), δ68.0 (—CH₂CF₂—, t), δ70.4 and 71.9(—OCH₂CH₂O—), δ70.9-71.3 (—CH₂— for ME2Ox), δ73.4 (backbone —CH₂— forFOx), δ74.0 (backbone —CH₂— for ME2Ox), δ75.3 (—CH₂— for FOx),δ110.0-123.3 (—CF_(n)CF₃).

Table 5 lists the molar ratios of monomer feed as well as thecompositions of polymers. Monomer/1,4-butanediol ratios were varied inorder to make polyoxetanes with differing molecular weights. The degreeof polymerization (D_(p)) and equivalent molecular weight are determinedby end group analysis as described above. The BF₃—OEt₂/1,4-butanediolratio was kept constant at 2.2/1, and in all compositions in Table 5,the reactions were done under nitrogen atmosphere with a temperature at0-5° C. Monomer ratios in copolymers are very close to feed ratios.

GPC results are also listed in Table 5. The number average molecularweights (M_(n)) correlate well with end group analysis results for ME2Oxhomo- and ME2Ox/FOx copolymers, but show higher values for 5FOxhomopolymer. The molecular distribution has a trend that thepolydispersity (M_(w)/M_(n)) decreases as monomer/co-catalyst ratioincreases for all polymer series. When the monomer/co-catalyst ratio isabove 22, the polydispersities are 1.9-2.2. As shown in Table 5, theD_(p) of polymer is not directly related to the monomer/co-catalystratios. TABLE 5 Copolymerization of ME2Ox and FOx monomers via BF₃—OEt₂catalyst system at 0° C. in methyene chloride Polymers Sample Monomerfeed ratio [Monomer]/ ME2Ox/ Equiv. M_(n) ^(c) Name ME2Ox 5FOx 7FOx[co-catalyst]^(a) FOx D_(P) ^(b) MW ^(b) (/10³) M_(w)/M_(n) ^(c) M-1 1 —— 5.5 — 12.4 2540 3.4 2.7 M-2 1 — — 11 — 16.9 3450 3.6 3.2 M-3 1 — — 22— 18.6 3810 3.0 2.1 M-4 1 — — 33 — 18.2 3710 3.3 2.2 M5F-1 0.5 0.5 — 5.50.53/0.47 16.8 3680 4.0 2.6 M5F-2 0.5 0.5 — 11 0.54/0.46 17.9 3910 4.82.8 M5F-3 0.5 0.5 — 22 0.53/0.47 20.8 4570 4.7 1.9 M5F-4 0.5 0.5 — 330.52/0.48 20.6 4520 4.8 1.9 F-1 — 1 — 5.5 — 20.1 4720 8.7 2.4 F-2 — 1 —11 — 27.3 6390 11.6 2.1 F-3 — 1 — 22 — 31.9 7470 11.8 1.9 F-4 — 1 — 33 —36.8 8620 12.9 2.0 M7F-1 0.5 — 0.5 22 0.55/0.45 18.6 4550 5.3 2.2 M7F-20.67 — 0.33 22 0.66/0.34 14.9 3440 4.5 1.9^(a)Monomer to co-catalyst (1,4-butanediol) molar ratio,[BF₃—OEt₂]/[1,4butanediol = 2.2 (constant)^(b) Determined by ¹H-NMR end group analysis^(c)Determined by GPC

Thermal analysis. Glass transition temperatures (T_(g)'s) of thepolyoxetanes were measured using sub-ambient DSC. Table 6 shows T_(g) ofME2Ox and FOx homopolymers and their copolymers. ME2Ox homopolymer hasthe lowest T_(g) (−67° C.) close to the T_(g) of PTMO (ca, −70° C.).TABLE 6 Glass transition temperatures (Tg) for polyoxetanes Homo- orCopolymers Tg (° C.) ME2Ox −67.3 5FOx −43.5 7FOx −52.7 ME2Ox/5FOx (1/1)−56.9 ME2Ox/7FOx (1/1) −55.6 ME2Ox/7FOx (2/1) −58.3

The T_(g) of 5FOx homopolymer is approximately −44° C. From a scan ofphysical mixture of ME2Ox and 5FOx homopolymers, it was observed thatthis mixture has two T_(g)'s because the two homopolymers are completelyimmiscible. In contrast, ME2Ox/5FOx (1/1) copolymer gives one T_(g) at−57° C. in between the T_(g)'s of the homopolymers. This result supportsthe composition study of the copolymer that indicates a random oralternating tendency but not blocky sequence. The T_(g) of copolymer canbe estimated by the Fox equation using the T_(g)'s of homopolymers:T _(g(cal)) ⁻¹ =w ₁ T _(g1) ⁻¹ w ₂ T _(g2) ⁻¹where w₁ and w₂ are weight fraction of each component. Using W_((ME2Ox))and w_((5FOx)) and homopolymer T_(g)s, T_(g(cal)) is −54° C. forME2Ox/5FOx (1/1). Similarly, T_(g(cal)) of ME2Ox/7FOx (1/1) andME2Ox/7FOx (2/1) are −58 and −60° C., respectively. Calculated T_(g)sare close to those observed.

EXAMPLE 3

As a further example for synthesis of telechelics, FOx-MEnOx telechelicswere prepared where n=3 or 7. The purpose of this synthetic work was toprovide F-2/F-3 groups that would have a more hydrophilic character. Inshort, using ring opening polymerization as described above, polyoxetanetelechelics with hydrophobic semifluorinated and hydrophilicoligoalkylether pendant groups have been synthesized with random andblock sequences. Polyurethanes incorporating these novel telechelics assoft blocks have also been prepared. For the first time, the effect ofsoft block sequence distribution on polyurethane surface morphology andwetting behavior has been demonstrated. TM-AFM reveals surface nanophaseseparation for the polyurethane containing a block-oxetaneco-telechelic, while the polyurethane containing a random-oxetane softblock shows no surface microstructure. Wetting behavior is stronglyinfluenced by the surface nanoscale morphology. This observationsuggests that surface nanostructure must be taken into account fordemanding applications such as those requiring biocompatibility or“smart” behavior.

The reaction mechanism of cationic ring-opening polymerization (ROP) ofoxetane monomers using boron trifluoride (BF₃) has seen considerablestudy and the general features are known as described above. In thepresent work, modified reaction conditions were used to give telechelicshaving different monomer sequences. The goal of this work was to learnwhether monomer sequence distribution would affect surface properties ofderived polyurethanes.

The oxetane monomer 3-(2,5,8,11-tetraoxydodecyl)-3-methyloxetane(ME3Ox), a new compound, was synthesized from tri(ethylene glycol)monomethyether and 3-bromomethyl-3-methyloxetane (BrOx).Copolymerization of ME3Ox and 3-trifluoroethoxymethyl-3-methyloxetane(3FOx) were carried out by cationic ring opening polymerization usingBF₃ and butane diol co-catalysts. For the preparation of blockcopolyoxetane ME3Ox-block-3FOx, ME3Ox monomer was added to catalyst at0° C. for 4 hrs. Then a dilute solution (CH₂Cl₂) of 3FOx monomer wasadded dropwise slowly over 24 hrs. The reaction mixture was stirred more12 hrs, then quenched with water and the product isolated.

To obtain a blocky-type copolymer, monomer addition order and additionspeed were varied. When 3FOx monomer was polymerized first in thepresence of BF₃—OEt₂ and butane diol (BD) cocatalysts and the secondmonomer ME3Ox was added, a mixture of homo-telechelics as a two-phaseliquid mixture was obtained. Interestingly, when ME3Ox was added as thefirst monomer followed by 3FOx, the product was a one phase viscousliquid, indicating formation of a block copolymer (telechelic). Afterthe reaction of first monomer ME3Ox, Mn determined by end group analysiswith trifluoroacetic anhydride is 2,600. Then, after slow addition ofsecond monomer 3FOx, Mn=4,200 for the final telechelic. A parallelincrease in Mw by GPC was obtained. Table 7 contains compositions andcharacterization data. TABLE 6 End gp GPC Molecular weight (10⁻³) DSCMDSC Telechelic polymers (10

) Mn Mw (Pd) cyc % Tg Tc/Tm Tg1 PTMO 2.2 3.7 6.8 1.9 ? ?′ −78.1 3FOxhomo 7.1 13.9 21.6 1.5 20 −47.6 — −47.4 5FOx homo 7.5 — — — −45.9 — —7FOx homo — — — — −54.6 — — ME2Ox homo 3.8 3.0 6.3 2.1 −68.0 — —ME2Ox./0 FOx (1/1) 3.8 2.3 7.5 3.2 −57.7 — — ME2Ox./5 FOx (1/1) 1.6 1.78.9 1.9 −58.1 — — ME2Ox./7 FOx (1/1) 1.5 7.5 12.6 1.7 −56.9 — — ME2Ox./7FOx (2/1) 3.1 6.1 9.6 1.6 −58.5 — — ME3Ox homo 3.0 0.7 3.2 4.6 −75.8 —−74.2 ME3Ox./3 FOx (1/1) 3.1 1.6 4.3 2.6 12 −69.9 — −61.8ME3Ox-block-3FOx (2/3) 4.2 1.6 4.1 2.6

−61.8 — −59.7 ME3Ox-block-3FOx (2/1) 1.9 0.8 3.5 4.5 −70.7 — −69.0 ME7Oxhomo 3.2 1.0 2.7 2.7 −71.8 −52/16 — ME7Ox.(3 Fox (1/1) 5.8 2.4 5.1 2.1−66.9 −30/16 — ME7ox-block-3FOx (2/3) 5.2 3.2 5.2 1.6 −64.8 −28/13 —ME7Ox-block-3FOx (2/1) 3.5 1.9 1.5 1.4 −70.5 −48/16 — ME2Ox homo + 5FOxhomo — — — —

— — ME3Ox homo + 3FOx homo — — — — — — −59.8/−67.9

Molecular weight (10⁻³) DSC MDSC Polyurethane wt % Mn Mw Pd Tg1 Tg2 Tg1Tg2 PTMO/MDI./BD 61 37.5 142.9 3.8 ? ? −70.3 56.6 (ME3Ox homo)/MDI./BD50 — — — (?) 49.7 — — (ME3Ox/3FOx)(1/1)/MDI./BD 74 — — — −38.8 (?) — —(ME2Ox/5FOx)(1/1)/MDI./BD 74 — — — −41.8 (?) — —(ME2Ox/5FOx)(1/1)/MDI./BD 15 — — — — — — — (ME3Ox homo)/MDI./BD 63 7.814.1 1.8 −43.8 (?) −36.8 129.9? (ME3Ox/3FOx)(1/1)/MDI./BD 73 3.1 24.32.7 −41.2 (?) −36.8 ? (ME3Ox-/2-3FOx)(2/3)/MDI./BD 68 7.4 15.2 2.1 −41.3(?) −38.4 65.1 (ME7Ox homo)/MDI./BD 69 6.5 10.0 1.6 −55.9 (?) — —(ME7Ox/3FOx (1/1)/MDI./BD 58 6.0 10.1 1.7 −46.4 (?) — —(ME7Ox-/2-3FOx)(2/3)/MDI./BD 66 6.3 12.3 2.0 −44.4 (?) — — (3Foxhomo)/MDI./BD 71 13.4 13.1 3.2 — — −39.9 59.9 (Mtc.ME3Ox +3FOx)(1/1)/MDI./BD 70 7.9 16.0 2.0 — — −59.3/−42.5 ?GPC molecular weight determinations on telechelics usually showed thepresence of a peak corresponding to cyclic tetramers. [Malik, A. A.;Archibald, T. G.; GenCorp: US, 2000] The percent cyclics present in thepresent work (0-20%) is not reproducible. Samples examined by DSC and¹⁹F-NMR contained cyclics but the qualitative conclusions are deemedvalid. Furthermore, once telechelics are used to prepare PUs, cyclicsare removed by purification procedures, as the telechelics arenonfunctional and relatively nonpolar.

To investigate structural differences, ¹⁹F-NMR spectra were obtained.The 3FOx CF₃— peaks in block and random copolymers shift to low fieldrelative to 3FOx homopolymer. A similar small chemical shift is observedwhen ME3Ox homopolymer is admixed with 3FOx homopolymer solutions,indicating the shift for copolymers is largely a solvent effect. Acomparison of the relative peak shapes is revealing. Homo- andblock-telechelics show a series of well-resolved peaks with J_(1H-19F)=8Hz. In contrast, the random copolymer peak is broad with littleresolvable structure. This observation supports the hypothesis that therandom telechelic is comprised of random sequences with many sequencedistributions. In contrast, the block co-telechelic contains (3-FOx)_(n)sequences that mimic those in the homo-telechelic. Hence 3FOx andME3Ox-block-3FOx telechelics have similar ¹⁹F-NMR spectra.

Polyurethanes were prepared using polyoxetane telechelics or a referencePTMO soft segment as described above for ME2Ox and FOx-BrOx telechelics.In brief, methylenediphenyldiisocyanate (MDI) and butane diol (BD) wereused for hard segment with ME3Ox/3FOx copolymer soft segment.Polyurethanes were prepared via solution reaction in dimethylacetoamide(DMAc) using a two-step method (first, MDI plus soft block telechelic;second, BD chain extender). Poly(tetramethylene oxide) (PTMO),M_(n)=2,000, was used as soft block for a standard segmentedpolyurethane as a control sample.

FIG. 8 shows the structure and ¹H-NMR spectrum of a representative PU,MDI/BD(27)/ME3Ox-ran-3FOx(1:1), PU-1 in DMSO-d6. Polyurethanes aredesignated: isocyanate/chain extender (hard segment wt %)/soft segmentmonomer 1-sequence-soft segment monomer 2 (mole ratio). Othercompositions were also determined by ¹H-NMR spectra:MDI/BD(32)/ME3Ox-block-3FOx(2:3), PU-2, and MDI/BD(36)/PTMO, PU-3. Glassslides were dip-coated from 20% DMAc solutions. The dip-coated PU filmswere prepared on glass slides from 20% dimethylacetamide (DMAc) at roomtemperature, dried at 60° C. for 5 h at ambient pressure, followed at80° C. for 2 days under vacuum.

Tapping-mode AFM (TM-AFM) is a powerful method for evaluating polymersurface morphology. FIGS. 9 a-f show TM-AFM images of PU filmscontaining PTMO (PU-3), ME3Ox-ran-3FOx copolymer (PU-1), andME3Ox-block-3FOx copolymer (PU-2). The surfaces of all films aretopologically quite flat (FIGS. 9 a, c, e) with RMS roughness (R_(q))less than 1 nm. Phase images of the three films are clearly different(FIGS. 9 b, d, f). Although tapping forces are relatively weak(A/A₀=0.83-0.92), phase images for PU-3 (FIG. 9 b) and PU-2 (FIG. 9 f)show strong contrast characteristic of nanoscale phase separation.

The surface of PU-3 (FIG. 9 b) has phase separation on the order of 10nm due to the hard and soft segments as shown schematically. Thistypical PU phase segregation has been observed previously. [Garrett, J.T.; Siedlecki, C. A.; Runt, J. Macromolecules 2001, 34, 7066-7070] Thephase image of PU-1 containing the ME3Ox-ran-3FOx telechelic isfeatureless (FIG. 9 d). This is consistent with a surface structurewhere the random-soft block predominates. With increased tapping force(A/A₀=0.5-0.6) a phase-separated structure appears in the phase image(data not shown), reflecting the presence of sub-surface hard blocks.

In contrast, TM-AFM of PU-2 containing the block-soft segment (FIG. 9 f)shows strong nano-phase separation that is attributed to two blockdomains, viz., ME3Ox and 3FOx. We use a conventional interpretation ofmodulus-sensitive phase images at light tapping where the lighter colorportions are assigned to the organized domain, in this case 3FOx. [Uilk,2002 #533] The average domain size is about 20 nm in diameter, largerthan the hard- and soft-segment segregation observed in PU-3 (FIG. 9 b).The observed phase separation must reflect the immiscibility of the 3FOxand ME3Ox block segments in the liquid phase, as the blocks are 75° C.(3FOx) and 100° C. (ME3Ox) above T_(g).

The interesting difference in nanoscale surface phase separation for PUscontaining random and block co-telechelics is reflected in contrastingwetting behavior. For evaluation of surface wetting properties, dynamiccontact angle (DCA) analysis by the Wilhelmy plate method was used asdescribed in Uilk, J. M.; Mera, A. E.; Fox, R. B.; Wynne, K. J.Macromolecules 2003, 36, 3689-3694.] The RMS roughness, R_(q), is lessthan 1 nm for all coatings. Thus surface roughness cannot contribute toadvancing (θ_(adv)) or receding (θ_(rec)) contact angles or contactangle hysteresis (deltaθ).

As a point of reference, PU-3 containing the PTMO soft segment wasexamined. PU-3 has a θ_(adv) of 93° and a θ_(rec) of 49°. From previouswork [Lamba, N. M. K.; Woodhouse, K. A.; Cooper, S. L. In Polyurethanesin Biomedical Applications; CRC Press: Boca Raton, Fla., 1998, p 15.]and our experience, θ_(adv), θ_(rec), and delta θ(44°) are fairlytypical values for PTMO PUs. The moderate deltaθ(44°) is largelyattributed to rapid surface reorganization of the low T_(g) PTMO softblock, though TM-AFM suggests there may be a near-surface hard blockcontribution as well.

One approach to analysis of chemically heterogeneous surfaces usingwetting behavior is to compare an “AB” surface to that of A and B alone.Several well-known methods exist to analyze nonideality responsible forsurface behavior. Here, we use a qualitative comparison of cotelechelicPUs with corresponding homo-telechelic PUs. Homo-telechelic compositionsand contact angles are: MDI/BD(29)/3FOx: θ_(adv), 110°, θ_(rec), 70°;MDI/BD(37)/ME3Ox; θ_(adv), 93°, θ_(rec), 32°.

Analysis of PU-1 containing the ME3Ox-ran-3FOx soft segment gaveθ_(adv)=104°, θ_(rec)=39°, and deltaθ=65°. The PU-1 surface ishydrophobic in air due to fluorinated groups with θ_(adv) similar to thePU 3FOx homopolymer. However, PU-1 is hydrophilic in water (θ_(rec),39°) with a receding contact angle closer to ME3Ox PU (32°) than to 3FOxPU (70°). Clearly, extensive surface reorganization occurs in waterfavoring hydrophilic ether side groups at the water polymer interface.The result is a very large contact angle hysteresis.

For PU-2 containing ME3Ox-block-3FOx, θ_(adv) (106°) is also close toθ_(adv) for the PU 3FOx homopolymer. In this regard, PU-2 and PU-1 aresimilar. However, θ_(rec) (56°) is 17° higher than PU-1 (θ_(rec), 39°)resulting in a smaller contact angle hysteresis for PU-2 (50°) comparedto PU-1 (65°). This result indicates the PU-2 surface is hydrophobic inair like the PU 3FOx homopolymer and only moderately hydrophilic inwater, more like the PU 3FOx homopolymer than PU ME3Ox. Clearly, thenanophase separated PU-2 surface structure is more hydrophobic overallthan the corresponding random-soft block surface. This amplification ofhydrophobicity occurs for PU-2 even though the fluorinated nano-domainsdo not cover the whole surface (TM-AFM, FIG. 9 f). Over the limited timescale investigated thus far, the self-assembly responsible forfluorinated surface nanodomains apparently inhibits access of asignificant fraction of near-surface, more hydrophilic polyether sidechains to water.

This Example demonstrates for the first time, the effect of soft blocksequence distribution on surface morphology and wetting behavior.Surface nanophase separation is observed for PU-2, which contains ablock-oxetane co-telechelic, while PU-1, which contains a random oxetaneco-telechelic, shows no surface microstructure. Surprisingly, wettingbehavior is strongly influenced by nanoscale surface morphology. Thisobservation suggests that surface nanostructure must be taken intoaccount for demanding applications such as those that requirebiocompatibility or “smart” behavior.

Surface Activity of MeNOx/FOx polyurethanes. While the surfaceproperties of the SM's are interesting by themselves, a key question is“will surface properties be conferred to a substrate polymer”. FIG. 10shows a striking example of conferring surface properties to a substratepolymer. Here, only 2% MDI/BD/(ME3Ox-ran-3FOx)(1:1) (PU-1) and 2%MDI/BD/(ME3-block-3FOx)(1:1), PU-2 respectively are added to a typicalbase polyurethane, MDI/BD(36)/PTMO. FIG. 10 unequivocally shows that thephase separated nanoscale morphology of MDI/BD/(ME3Ox-block-3F)(1:1),PU-2 seen in FIG. 9 f is conferred at a 2% loading level to theconventional MDI/BD(36)/PTMO polyurethane. Wetting behavior on the 2%modified material (shown only for the parent PU-2) is similar to theparent PU-2 and confirms that the SM PU-2 is surface concentrated.Furthermore, X-ray photoelectron spectroscopy confirms the presence of ahigh level of fluorine in the top 30 nm, consistent with a high3FOx-like concentration.

In contrast, at a loading of 2% PU-1, MDI/BD/(ME3Ox-ran-3FOx)(1:1)loading level to the conventional MDI/BD(36)/PTMO polyurethane, arelatively featureless nanoscale morphology is seen, as for the parentMDI/BD(27)/ME3Ox-ran-3FOx(1:1), PU-1 (FIG. 9 d). Wetting behavior on the2% modified material (shown only for the parent PU-1) is similar to theparent PU-1 and confirms that the SM PU-1 is surface concentrated.Furthermore, X-ray photoelectron spectroscopy confirms the presence ofan intermediate level of fluorine in the top 30 nm, consistent with ahigher functional group (F2, hydrophilic MEnOx) concentration.

These results are of the utmost importance in demonstrating that the SMindeed modifies the surface of the commodity-like, conventionalMDI/BD(36)/PTMO polyurethane. Importantly, the wetting behavior of theconventional MDI/BD(36)/PTMO polyurethane is modified by 2%incorporation of the SMs in the manner expected (data not shown).

EXAMPLE 4

Reaction on polymer example: substitution of 5,5-dimethyl hydantoin ontoIPDI-BD(40)/3FOx:BrOx-1:1(4700), PU-4, from Example 1, Table 3.: Thesubstitution reaction was carried out in dimethyl formamide (DMF).5,5-Dimethyl hydantoin, DMH, (2.55 g, 19.90 mmol) was introduced into3-neck round bottom flask with DMF (15.30 g). Then potassium carbonate,K₂CO₃, (11.06 g, 80.02 mmol) was added into the medium. K₂CO₃ is notsoluble in DMF; it was suspended in the solvent. The mixture was heatedand stirred (stirring bar) under nitrogen purge and with condenser for 1hour. Then PU (12.27 g, 0.26 mmol) in DMF (21.01 g) was added toreaction medium drop wise. The reaction temperature was kept around90-95° C. for 42 hours. The reaction was then terminated by cooling toroom temperature. The mixture was precipitated into methanol/water (4:1)solution in order to get the final product. The resulting polyurethanewas precipitated out of the solution. The degree of substitution andfinal yield was obtained by NMR (about 70%).

This polyurethane SM is designated 36 in FIG. 7. We refer to thematerial obtained by treatment of a coating of 36 alone with bleach as36B. We refer to the composition obtained by adding 2% 36 to the bulk PU42. First, we consider the remarkable properties of 36 alone.

As shown in FIG. 11, coatings designated as 36 in FIG. 7 haveunexpectedly unprecedented wetting behavior. All prior art demonstratesthat polymers exposed to water either have no change in wetting behavior(e.g., polyethylene, polypropylene, poly(tetrafluoroethylene) due tototal lack of interaction with water, or else become apparently morehydrophilic. The latter behavior is found for polymers that have someinteraction with water such as nylons and polyurethanes. [Pike, J. K.;Ho, T.; Wynne, K. J., Water-induced surface rearrangements ofpoly(dimethylsiloxane-urea-urethane) segmented block copolymers,Chemistry of Materials, 1996, 8, 856-860.]

As shown in FIG. 11, a coating of 36 becomes more hydrophobic whendipped in water or, if dry initially, becomes more hydrophobic ifexposed to a humid atmosphere. FIG. 11 shows a procedure devised todemonstrate the new “contraphilic” behavior. FIG. 12 shows the Wilhelmyplate data and, for simplicity, the visually determined wetting behaviorusing the conventional sessile drop method. In this case, a picture ofthe drop was taken (on a separate but identical sample) at importantpoints in the procedure to illustrate the unprecedented contraphilicbehavior.

Stage 1. With reference to FIGS. 11 and 12, Stage 1 is the first contactof water with the coating. Observation of the shape of the drop with thecontact angle less than 90 degrees illustrates that the coating ishydrophilic. This is quantitatively determined (82 deg) from theWilhelmy plate data and is obtained as shown in FIG. 11 from the firsttime the coating is immersed in liquid water.

Stage 2. The coating is withdrawn from water. The low receding contactangle (θ_(rec)) that is seen visually as the drop is withdrawn into thesyringe can be calculated quantitatively from the Wilhelmy recedingforce distance curve (about 40 deg).

Stage 3. The coating is re-immersed in water. Remarkably, the advancingcontact angle (θ_(adv)) has increased to over 100°. This is easily seenvisually in the picture of the drop re-impinging on the same surfacealready wetted by water in Stage 1. The change in the wetting behavioris quantitatively measured by the Wilhelmy advancing force distancecurve (108°). Again, a coating becoming more hydrophilic when simplyimmersed in ambient temperature water is unprecedented. Furthermore, thechange is not just a few degrees but 10's of degrees and is clearlyvisible.

Stage 4. When the coated slide is immersed further than the originaldepth, the Wilhelmy plate curve suddenly changes. Suddenly, water isimpinging on a surface that has not seen liquid water. The wettingbehavior changes back to hydrophilic, as seen in Stage 1. This change iseasily observed visually. When the circumference of the dropre-impinging on the surface exceeds the circumference originally wetted,the contact angle of the drop changes from greater than 90 degrees(hydrophobic) to less than 90° (hydrophilic).

If the coating is dried in an oven (60° C.), hydrophilic behavior isonce more seen and the contraphilic behavior is reinstated. If thecoating is kept at ambient humidity and temperatures, the wettingbehavior depends on humidity.

Because the change in wetting behavior is observed by testing thecoating in water, the receding contact angle is always the same.

Contraphilic behavior is a completely new phenomenon. Again,surprisingly, preliminary evidence suggests that certain of theMEnOx-FOx polyurethanes are contraphilic, particularly polyurethanesmodified with 2% ME7Ox-3FOx.

EXAMPLE 5

Example 5 is an extension of the “reaction on polymer” approach ofExample 4 to create a biocidal surface by means of an SM. In thisexample, SM 36 is added to a substrate polyurethane (sometimes referredto as a “base” PU), and the surface is exposed to hypochlorite (dilutebleach) as shown in FIG. 7. The resulting coating is biocidal by virtueof the presence of the biocidal SM.

Preparation of Blends and Biocidal Coatings. Polyurethane blendscontaining 2-wt % dimethylhydantoin (DMH) substituted PU (36) and 98-wt% conventional polyether (PTMO) PU were prepared in tetrahydrofuran(THF). The sample films for anti-bacterial tests were prepared by simplydip-coating glass cover slips (Corning, 24×40×1.2 mm) and distributingthe polyurethane evenly over both sides. The samples were placed in anupright position at ambient conditions for 24 hours and in the ovenovernight at 60° C. under reduced pressure. The resulting films weretransparent with no visible roughness.

Anti-bacterial Tests: For anti-bacterial activity tests a modifiedversion of AATCC 100 method was employed. FIG. 13 schematically showsthe testing procedures. The coated cover glass slides were soaked into asolution of free chlorine (50% Clorox® solution containing 3% sodiumhypochlorite) for 1 hour. Then they were rinsed with deionized (D.I.)water and placed into vacuum for overnight (60° C., 4 Torr). A knownvolume of inoculum containing bacteria (e.g., E. Coli) at aconcentration of about 10⁷-10⁸ CFU (Colony Forming Units)/ml was usedfor biocidal test. Slides of base PU (PTMO based PU) were used ascontrol. The initial bacteria inoculum was diluted with saline solution(10 folds). So, this aqueous suspension contains 106-107 CFU/ml ofbacteria. 1 microliter of this suspension was placed into surface of thecoated glass slide. The slide was then sandwiched with an identicalslide. For complete contact the “sandwich” was squeezed and a weight(beaker) was placed on the top. After different contact times (1, 1.5,and, 2 hours) the entire sandwich system was placed into aqueous sodiumthiosulfate (10 ml, 0.03 wt %) solution. The resultant solution was thenshaken for 5 min. An aliquot of the solution was then serially diluted(3 times) and 100 microliters of each dilution was plated on to anutrient agar plate. Bacterial colonies on the agar plates were countedafter incubation at 37° C. for 24 hours.

A typical test utilizing an E. coli challenge is shown in FIG. 14. Inparticular, the PU control had greater than 400 cfu's while the 98% PU,2% biocidal SMA had 0 cfu's. All bacteria were killed in thirty minuteswith a minimum of 99.9% or 3.6 log reduction.

FIG. 15 summarizes a test challenge using a Pseudomonas aeruginosa. Amodified AATCC-100 “sandwich” test was utilized wherein the bacterialchallenge is confined between two coated surfaces as discussed above inconnection with FIG. 8. To provide a more challenging challenge than theE. coli test, the bacterial stock solution was not diluted and a 10times higher volume of test solution was used. With a challenge of10⁶-10⁷ CFUs for only 15 min, no surviving colony forming units (CFUs)were seen. In particular, the culture dish images of FIG. 10 demonstrateno surviving P. aeruginosa CFU's after a 30 min challenge to Gen-1 2%SMA-PU coating. The exponential growth after 24 hr development (upperright) is evident on the control pre-biocide SMA modified PU. Incontrast, there are no surviving CFU's after N-Cl formation by bleachactivation of the Gen-1 2% SMA-PU coating.

In a similar test, coatings were challenged against Staphylococcusaureus. Again, the modified AATCC-100 “sandwich” test was utilized (FIG.8) wherein the bacterial challenge is confined between two coatedsurfaces. With a challenge of 10⁶-10⁷ CFUs for only 30 min, no survivingcolony forming units (CFUs) were seen.

While the SM concept was validated with a prebiocidal (Example 4) orbiocidal (Example 5) moiety, 5,5-dimethylhydantoin, it will beunderstood by those who are skilled in the art that the functionalgroups surface-concentrated by the approach described above is broad.For example, the functional groups “F-3” shown in FIG. 5 may be a broadvariety of hydantoin-like moieties that optimizes biocidal activity(e.g., those described in U.S. Pat. No. 6,469,177 to Worley which isincorporated by reference). Other moieties that could easily beenvisaged include alkylammonium species that are known to have biocidalproperties. [Tiller, J. C.; Lee, S. B.; Lewis, K.; Klibanov, A. M.,Polymer surfaces derivatized with poly(vinyl-N-hexylpyridinium) killairborne and waterborne bacteria, Biotechnology and Bioengineering,2002, 79, 465-471.]

Alternatively, F-3 could be a dye molecule that would protect theunderlying polymer from UV degradation. F-3 could be a moiety suchas—OSi(OR)₃ that would convert to siliceous functionalization in thepresence of moisture. F-3 could be a bioactive moiety such as a peptidesequence that would favor biocompatibility. In this regard, F-3 could bethe RGD peptide sequence that favors endothelialization.

The remarkable and unexpected surface properties of polymers containingsoft blocks of the general structure shown in FIG. 2 demonstrates thenon-obviousness of compositions employing this molecular architecture.The ability of polymers of the general structure shown in FIG. 2 is notcompletely understood and we are not bound by theory to explain theobserved results. Nevertheless, it appears that the ability of polymerscontaining soft blocks of the general structure described in FIG. 2 tomodify the surface behavior of a “base” polymer, even when present atlow weight percent apparently stems from (a) the tendency of soft blocksto concentrate at the surface, (b) the presence of the surface-philicgroup, (c) the low glass transition temperature of soft block thatfacilitates (i) chemical modification (as in reaction on polymer shownin Example 4 or even reaction on polymer surface, as shown in Example 5)(ii) rapid surface reorganization that causes a kind of “compliance” tothe medium to which the polymer is exposed (seen in high contact anglehysteresis), and facile, reversible interaction with a medium as seen inunprecedented “contraphilic” behavior discussed in Example 3, and (d) asyet little understood phenomena such as (i) described in Example 1,where the polyurethanes containing co-telechelics have higher θ_(adv)and lower θ_(rec) than the parent homo-telechelic PUs and (ii) where anew synthetic procedure in Example 2 led to the discovery ofamplification of hydrophobicity, which occurred when the cotelechelichad a block structure of fluoro-groups (F 1) rather than a randomstructure of F 1 groups.

While the invention has been described in terms of its preferredembodiments, those skilled in the art will recognize that the inventioncan be practiced with modification within the spirit and scope of theappended claims.

1. A method of producing a polymeric article or coating with a surfaceactive property, comprising the steps of: forming a surface activepolymer or macromonomer having a first segmer that favors migration tothe surface of a bulk polymer, and a second segmer which enables anactivity of interest; and combining said surface active polymer withsaid bulk polymer to produce a polymeric article having the surfaceactive polymer concentrated primarily on the surface of the said bulkpolymer.
 2. The method of claim 1 wherein said first segmer is afluorinated group.
 3. The method of claim 1 wherein said first segmer isselected from the group consisting of —(CH₂)n(CH₂)m or —(CH₂)nCF₂)mHwhere n ranges from 1 to 10 and m ranges from 1 to
 12. 4. The method ofclaim 1 wherein said activity of interest is biocidal.
 5. The method ofclaim 1 wherein said activity of interest alters the surface wettabilityof said bulk polymer.
 6. The method of claim 1 wherein said activity ofinterest provides an indicator.
 7. The method of claim 6 wherein saidindicator is selected from the group consisting of color change,fluorescence, phosphorescence, and chemiluminescence.
 8. The method ofclaim 1 wherein said activity is a modifiable leaving group.
 9. Themethod of claim 1 wherein said surface active polymer and said bulkpolymer are both polyurethanes.
 10. The method of claim 1 wherein saidfirst and second segmers are present on a soft block. 11-21. (canceled)22. 3-(methoxyethoxyethoxymethyl)-3-methyloxetane. 23.3-(2,5,8,11-tetraoxydodecyl)-3-methyloxetane.
 24. A contraphilicpolymeric material which is hydrophilic when dry and hydrophobic whenwet.
 25. A polymer material or coating comprising: isophoronediisocyanate/butane diol hard blocks; and soft blocks comprised offluorinated segmers combined with biocidal moieties.
 26. An oligomericor polymeric detergent or surfactant, comprising oleophilic groups,hydrophilic groups, and fluorous groups.
 27. The oligomeric or polymericdetergent or surfactant of claim 26, wherein said oleophilic groups areselected from the group consisting of —(CH₂)nH, tetramethylene oxide,isomeric hydrocarbon and hydrocarbon-halocarbon (—ChxCly)nH, and ketonecontaining side chains, where n ranges from 1-20, and x and y range from1 to
 2. 28. The oligomeric or polymeric detergent or surfactant of claim26 wherein said hydorphilic groups are selected from the groupconsisting of oligomeric and polymeric ethylene oxide, alcohol,carboxylic acid, and amine containing side chains.
 29. The oligomeric orpolymeric detergent or surfactant of claim 26 wherein said fluorousgroups are selected from the group consisting of —(CH₂)n(CH₂)mF and—(CH₂)n(CF₂)mH) where n ranges from 1 to 10 and m ranges from 1 to 12.30. The oligomeric or polymeric detergent or surfactant of claim 26wherein said oleophilic, hydrophilic, and fluorous groups are nonionic.31. The oligomeric or polymeric detergent or surfactant of claim 26further comprising a cationic or anionic functionality associated one ormore of said oleophilic, hydrophilic, and fluorous groups.